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EP1173490B1 - Copolymers with amphiphilic sub-units, a method for producing the same and the use thereof - Google Patents

Copolymers with amphiphilic sub-units, a method for producing the same and the use thereof Download PDF

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Publication number
EP1173490B1
EP1173490B1 EP00936690A EP00936690A EP1173490B1 EP 1173490 B1 EP1173490 B1 EP 1173490B1 EP 00936690 A EP00936690 A EP 00936690A EP 00936690 A EP00936690 A EP 00936690A EP 1173490 B1 EP1173490 B1 EP 1173490B1
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EP
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Prior art keywords
component
ester
alkylene oxide
acid
use according
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EP00936690A
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German (de)
French (fr)
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EP1173490A1 (en
Inventor
Johann Klein
Kai Böge
Klaus Friedrich
Thomas Möller
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/20—Esters containing oxygen in addition to the carboxy oxygen

Definitions

  • Polymers are often certain technical Adapted to the requirements by the polymerization Monomer mixture is used.
  • the polymerization of a mixture two or more monomers is often called copolymerization denotes and leads, for example, to copolymers with two different types of monomers or terpolymers according to Use of three different types of monomers.
  • Copolymerization denotes and leads, for example, to copolymers with two different types of monomers or terpolymers according to Use of three different types of monomers.
  • Polymers often have certain technical properties Dependence on the selected comonomer ratio and the selected Set comonomers.
  • binders In the production of surface coatings or adhesives binders are often used, such as those caused by free radicals Polymerization of one or more radically polymerizable Monomers are available. Property variations are usually carried out according to the procedure given above, i.e. by Copolymerization of suitable monomers.
  • Emulsion polymerizations for example emulsion polymerization of vinyl acetate, often require the addition of a protective colloid. A such a process step delays the process flow, on the one hand others incur additional manufacturing process costs.
  • the invention was therefore based on the object of a copolymer To be available that can be manufactured without complex work steps and leads to flexible adhesive films when used in adhesives, which, however, is also excellent on hydrophilic substrate surfaces Have liability.
  • a copolymer that by radical copolymerization of at least two components A and B is available, with component A being a carboxylic acid ester an unsaturated carboxylic acid with an alkylene oxide adduct and as Component B is another free-radically polymerizable monomer is used.
  • a "copolymer” is used in the context of the present text Polymer understood that by radical polymerization of two or more radically polymerizable monomers is available. It can be a statistical copolymer, i. that is, the Sequence of the monomers is not subject to any particular order, it can However, it is also an alternating or a block copolymer act.
  • Copolymers used according to the invention have a component A and copolymerized a component B.
  • component A at least an ester of an at least difunctional and at least one olefinic carboxylic acid having unsaturated double bond with a Alkylene oxide adduct used.
  • the at least one have olefinically unsaturated double bond are suitable for example maleic acid, fumaric acid, itaconic acid, arconitic acid, 3,4,5,6-tetrahydrophthalic acid, crotonic acid, or a mixture of two or more of it.
  • the Estem underlying olefinically unsaturated di- or polycarboxylic acids for example, are only partially esterified, i.e. only part of the available for an esterification with carboxylic acid groups esterified with a suitable alkylene oxide adduct. It is beyond that as well possible, the carboxylic acid groups of the carboxylic acid partially or completely react with an alkylene oxide so that the ester function by Oxalkylation is formed.
  • Suitable partial esters as used in a preferred embodiment of the present invention are used as component A, are, for example, partial esters of the above-mentioned carboxylic acids with alkylene oxide adducts of linear or branched, saturated alcohols, which have at least 8 carbon atoms.
  • Suitable alcohols are for example the fatty alcohols with at least 8 carbon atoms, such as, for example by reducing natural fats or oils or by Reduction of fatty acids available from natural fats or oils or fatty acid cuts or their derivatives, for example their Esters with alcohols with 1 to 4 carbon atoms are available.
  • Fatty alcohols particularly suitable for producing the alkylene oxide adducts examples include octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, Dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, Hexadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, Guerbet alcohols, unsaturated fatty alcohols such as 12-hydroxystearyl alcohol, or higher Homologs of such alcohols with up to about 44 carbon atoms.
  • the alkyl group the fatty alcohols can be linear or branched, saturated or unsaturated his.
  • suitable alkoxylatable compounds are, for example Dialkylamines with linear or branched, saturated or unsaturated Alkyl radicals with a total of at least about 8 carbon atoms, linear or branched, saturated or unsaturated carboxylic acids, for example fatty acids, with at least about 8 carbon atoms, linear or branched, saturated or unsaturated acid amides, for example fatty acid monoethanolamides, with at least about 8 carbon atoms as well as linear or branched, saturated or unsaturated alkylamines, for example fatty amines, which in Alkyl radical have at least 8 carbon atoms.
  • Alkoxylates or "alkylene oxide adducts” are used in the context of present text the reaction products of suitable nucleophiles, for example of appropriately functionalized ethers, amines, Carboxylic acids, carboxamides or alcohols with alkylene oxides 2 to about 44 carbon atoms, in particular about 8 to about 24 carbon atoms.
  • the alkoxylation to the alkylene oxide adduct with ethylene oxide.
  • Alkylene oxide adducts have an average of at least one molecule an alkylene oxide unit.
  • the invention should average the number of alkylene oxide units per Alcohol molecule at least about 1.5, especially at least about 2 be.
  • Component A is the partial ester of olefinically unsaturated dicarboxylic acids used as the alcohol residue an alkoxylate of an alcohol, a carboxylic acid, a carboxamide, a dialkylamine or a monoalkoxylate have an amine.
  • alkoxylates are used as alcohol residues, by alkoxylation of the compound on which the alkoxylate is based are available with ethylene oxide or propylene oxide or both.
  • the alcohol residues on which the partial esters are based have a preferred one Embodiment of the invention on amphiphilic properties.
  • Amphiphilic properties can often be determined by the HLB value characterize amphiphilic compound.
  • suitable alcohol components have, for example, an HLB value from about 1.5 to about 18, for example about 2 to about 14 or about 3 to about 12.
  • the alkylene oxide adduct underlying nucleophilic radical from about 12 to about 24 carbon atoms, for example, about 16 to about 20 carbon atoms.
  • the corresponding alkylene oxide adducts have about 1 to about 40 alkylene oxide units, for example about 2 to about 12 ethylene oxide or Propylene oxide units, or both
  • partial esters can be used in the form of their free acids however, the partial esters are also possible as salts, for example as Use alkali metal salts, or ammonium salts.
  • partial ester salts with volatile amines used for example salts with butylamine or triethanolamine. Salt formation can occur before or after the polymerization be performed.
  • Such full esters have at least one alkylene oxide adduct as the alcohol residue with a linear or branched, saturated or unsaturated alkyl radical with at least about 8 carbon atoms between the above Alkyl radical and the ester function derived from the unsaturated carboxylic acid at least 1 to about 40 alkylene oxide units, for example about 2 to about 12 alkylene oxide units.
  • Suitable alkylene oxide adducts have already been mentioned above.
  • the invention is the alkylene oxide units Ethylene oxide units or propylene oxide units or a mixture thereof, but especially ethylene oxide units.
  • the HLB value of a surfactant or emulsifier mixture can be determined from the values of its components calculate additively. Detailed lists of HLB values from retailers Available emulsifiers can be found, for example, at Fiedler, Lexikon of auxiliaries for pharmacy, cosmetics or related areas or at Kirk-Othmer (3.) 8, 910-918.
  • the half-ester is made from a carboxylic anhydride by adding the corresponding alkylene oxide adduct formed. If as component A a Half ester should be used, for example, the formation of the half ester in situ before or even during the copolymerization of the Components A and B are made by using an appropriate carboxylic anhydride and a corresponding alkylene oxide adduct or a mixture from two or more alkylene oxide adducts in the previously submitted Component B triggers.
  • component B in the context of the present invention at least one further radically polymerizable monomer used.
  • Suitable monomers are, for example, the vinyl esters of Carboxylic acids with about 2 to about 44 carbon atoms.
  • Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, the vinyl esters the isomeric pentanoic acids, hexanoic acids, heptanoic acids, octanoic acids, Nonanoic acids, decanoic acids and their higher homologues.
  • Component B is suitable, for example, ethylene or propylene.
  • the component lies A in the polymerization mixture to be copolymerized in an amount of about 0.01 to 70% by weight, for example in an amount of 0.5 to about 50% by weight or about 1 to about 20% by weight, based on the total Mixture, before.
  • the invention uses as component B vinyl acetate, vinyl propionate, Vinyl laurate or vinyl versatate, especially vinyl acetate, is used.
  • Component B is a mixture of two or more copolymerizable Monomers used. Mixtures of Vinyl acetate vinyl propionate, vinyl laurate or vinyl versatate, each with one or more of the other monomers specified above.
  • the mixture contains a preferred Embodiment at least one vinyl ester of a carboxylic acid, especially vinyl acetate.
  • the proportion of vinyl ester of a carboxylic acid should be at least about 30% by weight in such a mixture.
  • the copolymers used according to the invention can be prepared carried out according to the usual methods of radical polymerization.
  • the polymerization is preferred as an emulsion or Suspension polymerization carried out in water.
  • the Polymerization temperature is preferably about 50 to about 90 ° C, especially about 75 to about 85 ° C.
  • emulsifiers they can be used in the context of emulsion polymerization Usually used emulsifiers can be used. If necessary, a protective colloid can be added.
  • copolymers used according to the invention are, for example in adhesive preparations such as dispersion adhesives, pressure sensitive adhesives, at the production of adhesive films or for the production of Redispersion powders used.
  • the invention therefore also relates to the use of the Copolymers in a preparation containing at least 0.1% by weight of the Contains copolymers.
  • a preparation used according to the invention can in addition to copolymers according to the invention still up to about 50 wt .-% contain usual additives.
  • additives can for example the adhesive properties, the aging behavior, the Affect the setting process or the adhesion.
  • the glue can for example, contain so-called tackifier resins, which are usually divided into natural and synthetic (synthetic resins).
  • synthetic resins include, for example, alkyd resins, epoxy resins, melamine resins, Phenolic, urethane, hydrocarbon and natural Resins such as rosin, wood turpentine and tall oil.
  • To the synthetic Resins hydrocarbon resins, ketone resins, coumarone indene resins, Isocyanate resins and terpene phenolic resins.
  • the adhesives used according to the invention can be used Preparations contain solvents.
  • solvents are suitable as solvents for example monohydric or polyhydric alcohols with about 2 to about 10 carbon atoms.
  • the adhesives used according to the invention can be used Preparations contain defoamers.
  • defoamers for example defoamer based on fatty alcohol or silicone.
  • Preparations protective colloids such as polyvinylpyrrolidones, polyvinyl alcohols or contain cellulose or cellulose derivatives.
  • the preparation used as an adhesive according to the invention can contain stabilizers or antioxidants as additives.
  • stabilizers or antioxidants as additives.
  • the phenols for example the sterically hindered High molecular weight phenols, polyfunctional phenols, sulfur and phosphorus-containing phenols or amines.
  • hydroquinone hydroquinone methyl ether 2,3- (di-tert-butyl) hydroquinone, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydro xybenzyl-) benzene; Pentaerythritol tetrakis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; n-octadecyl-3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4,4-methylenebis (2,6-di-tert-butyl-phenol); 4,4-thiobis (6-tert-butyl-o-cresol); 2,6-di-tert-butyl phenol; 6- (4-hydroxyphenoxy) -2,4-bis (n-octyl-thio) -1,3,5-triazine; Di-n
  • the preparation used as an adhesive according to the invention can plasticizers such as benzoate plasticizers, phosphate plasticizers, contain liquid resin derivatives or vegetable and animal oils.
  • plasticizers such as benzoate plasticizers, phosphate plasticizers
  • liquid resin derivatives or vegetable and animal oils for example, sucrose benzoate and diethylene glycol dibenzoate are suitable and / or diethylene glycol benzoate, in which about 50 to about 95% of all Hydroxyl groups have been esterified, phosphate plasticizers, for example t-butylphenyl diphenyl phosphate, polyethylene glycols and their derivatives, for example diphenyl ether of poly (ethylene glycol), liquid resin derivatives, for example the methyl ester of hydrogenated resin, vegetable and animal oils, for example glycerol esters of fatty acids and their Polymerization products.
  • Plasticizers based on phthalic acid are also suitable, especially the alkyl phthalates.
  • the preparation used as an adhesive according to the invention can furthermore dyes such as titanium dioxide, fillers such as gypsum, talc, clay and the like and contain pigments.
  • emulsifiers or stabilizers or a mixture thereof contain.
  • Suitable emulsifiers are generally surfactants, the one have hydrophilic and a hydrophobic group. It can happen anionic emulsifiers, cationic emulsifiers or amphoteric Act emulsifiers.
  • Hydrocarbon emulsifiers with about 6 to about 22 carbon atoms, where the hydrocarbon chain is branched, unbranched, saturated, can be unsaturated, substituted, aliphatic or aromatic.
  • Another object of the invention is preferably the use as a binder in adhesive preparations.
  • Copolymer dispersion (Example 1) Homopolymer dispersion (Example 2) D1 12 N / mm 2 11.2 N / mm 2 tensile force 4.5 N / mm 2 15 N / mm 2 elongation at break 2200% 20 to 30%

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Peptides Or Proteins (AREA)

Abstract

Copolymers (I) obtained by radical copolymerisation of (A) ester(s) of at least difunctional carboxylic acids containing olefinic double bond(s) with alkylene oxide adducts and (B) other radically polymerisable comonomer(s). Independent claims are also included for (a) a process for the production of (I) by copolymerisation of at least two components (A) and (B) as above; (b) preparations containing at least 0.1 wt% (I).

Description

Die Erfindung betrifft die Verwendung eines Copolymeren, erhältlich durch radikalische Copolymerisation von mindestens zwei Komponenten A und B, wobei

  • a) mindestens ein Ester einer mindestens difunktionellen und mindestens eine olefinisch ungesättigte Doppelbindung aufweisenden Carbonsäure mit mindestens einem Alkylenoxidaddukt als Komponente A und
  • b) mindestens ein weiteres radikalisch polymerisierbares Monomeres aus der Gruppe Vinylester von Carbonsäuren mit 2 bis 44 C-Atomen, Ethylen oder Propylen als Komponente B
    • eingesetzt wird.The invention relates to the use of a copolymer obtainable by radical copolymerization of at least two components A and B, wherein
  • a) at least one ester of an at least difunctional and at least one olefinically unsaturated double bond carboxylic acid having at least one alkylene oxide adduct as component A and
  • b) at least one further radically polymerizable monomer from the group of vinyl esters of carboxylic acids having 2 to 44 carbon atoms, ethylene or propylene as component B.
    • is used.

    Eigenschaften von Polymeren werden häufig bestimmten technischen Erfordernissen angepaßt, indem bei der Polymerisation ein Monomerengemisch verwendet wird. Die Polymerisation eines Gemischs aus zwei oder mehr Monomeren wird häufig als Copolymerisation bezeichnet und führt beispielsweise zu Coplymeren mit zwei unterschiedlichen Monomertypen oder zu Terpolymeren entsprechend der Verwendung von drei unterschiedlichen Monomertypen. In solchen Polymeren lassen sich häufig bestimmte technische Eigenschaften in Abhängigkeit vom gewählten Comonomerverhältnis und den gewählten Comonomeren einstellen. Properties of polymers are often certain technical Adapted to the requirements by the polymerization Monomer mixture is used. The polymerization of a mixture two or more monomers is often called copolymerization denotes and leads, for example, to copolymers with two different types of monomers or terpolymers according to Use of three different types of monomers. In such Polymers often have certain technical properties Dependence on the selected comonomer ratio and the selected Set comonomers.

    So wird in der US 3,657,175 eine saure Latex-Zusammensetzung beschrieben, wobei das Copolymere aus einem Ester einer ethylenischen Polycarbonsäure und einem ethoxylierten Alkohol einerseits und Methacrylsäure sowie Styrol und/oder Butadien andererseits hergestellt wird. Diese Zusammensetzung wird als Verdicker verwendet.In US 3,657,175 an acid latex composition described, wherein the copolymer of an ester of an ethylenic Polycarboxylic acid and an ethoxylated alcohol on the one hand and Methacrylic acid and styrene and / or butadiene on the other hand becomes. This composition is used as a thickener.

    Bei der Herstellung von Oberflächenbeschichtungen oder von Klebstoffen werden häufig Bindemittel eingesetzt, wie sie durch radikalische Polymerisation von einem oder mehreren radikalisch polymerisierbaren Monomeren erhältlich sind. Eigenschaftsvariationen werden in der Regel gemäß der oben angegebenen Verfahrensweise durchgeführt, d.h., durch Copolymerisation geeigneter Monomerer.In the production of surface coatings or adhesives binders are often used, such as those caused by free radicals Polymerization of one or more radically polymerizable Monomers are available. Property variations are usually carried out according to the procedure given above, i.e. by Copolymerization of suitable monomers.

    Aus dem Stand der Technik ist es bekannt, die Flexibilität solcher Filme, beispielsweise von Klebstoffilmen, durch Verwendung von Comonomeren wie Dibutylmaleinat, Vinylversatat oder Acrylatestem zu verbessern. Nachteilig wirkt sich bei der Verwendung solcher Comonomerer jedoch aus, daß sich die Haftung von solchen Filmen oder Verklebungen auf polaren Oberflächen aufgrund der Hydrophobie der Comonomeren oft stark verschlechtert. Zudem besteht bezüglich der Kettenlänge in den Alkoholresten der eingesetzten Comonomeren eine Obergrenze dahingehend, daß Comonomere mit langkettigen Resten in der Regel einer Verwendung in der Emulsionspolymerisation nicht mehr zugänglich sind, da ihre Wasserlöslichkeit zu schlecht ist.It is known from the prior art that the flexibility of such films, for example of adhesive films, by using comonomers such as dibutyl maleate, vinyl versatate or acrylate testers. However, the use of such comonomers has a disadvantageous effect from that the liability of such films or sticking on polar surfaces often due to the hydrophobicity of the comonomers badly deteriorated. There is also a chain length in the Alcohol residues of the comonomers used an upper limit in that comonomers with long chain residues usually no longer accessible for use in emulsion polymerization because their water solubility is too poor.

    Emulsionspolymerisationen, beispielsweise die Emulsionspolymerisation von Vinylacetat, erfordern häufig die Zugabe eines Schutzkolloids. Eine solcher Verfahrensschritt verzögert zum einen den Verfahrensablauf, zum anderen entstehen zusätzliche Kosten für den Herstellungsprozeß. Emulsion polymerizations, for example emulsion polymerization of vinyl acetate, often require the addition of a protective colloid. A such a process step delays the process flow, on the one hand others incur additional manufacturing process costs.

    Der Erfindung lag daher die Aufgabe zugrunde, ein Copolymeres zur Verfügung zu stellen, das ohne aufwendige Arbeitsschritte herstellbar ist und bei einer Verwendung in Klebstoffen zu flexiblen Klebstoffilmen führt, die jedoch auch auf hydrophilen Substratoberflächen eine ausgezeichnete Haftung aufweisen.The invention was therefore based on the object of a copolymer To be available that can be manufactured without complex work steps and leads to flexible adhesive films when used in adhesives, which, however, is also excellent on hydrophilic substrate surfaces Have liability.

    Die oben genannten Aufgaben werden durch ein Copolymeres gelöst, das durch radikalische Copolymerisation von mindestens zwei Komponenten A und B erhältlich ist, wobei als Komponente A ein Carbonsäureester einer ungesättigten Carbonsäure mit einem Alkylenoxidaddukt und als Komponente B ein weiteres radikalisch polymerisierbares Monomeres eingesetzt wird.The above objects are achieved by a copolymer that by radical copolymerization of at least two components A and B is available, with component A being a carboxylic acid ester an unsaturated carboxylic acid with an alkylene oxide adduct and as Component B is another free-radically polymerizable monomer is used.

    Gegenstand der Erfindung ist damit die Verwendung eines Copolymeren, erhältlich durch radikalische Copolymerisation von mindestens zwei Komponenten A und B, wobei

  • a) mindestens ein Ester einer mindestens difunktionellen und mindestens eine olefinisch ungesättigte Doppelbindung aufweisenden Carbonsäure mit einem Alkylenoxidaddukt als Komponente A und
  • b) mindestens ein weiteres radikalisch polymerisierbares Monomeres aus der Gruppe Vinylester von Carbonsäuren mit 2 bis 44 C-Atomen, Ethylen oder Propylen als Komponente B
    • eingesetzt wird, als Bindemittel in Klebstoffzubereitungen, Dichtstoffen oder Redispersionspulvem. The invention thus relates to the use of a copolymer obtainable by radical copolymerization of at least two components A and B, wherein
  • a) at least one ester of an at least difunctional and at least one olefinically unsaturated double bond carboxylic acid with an alkylene oxide adduct as component A and
  • b) at least one further radically polymerizable monomer from the group of vinyl esters of carboxylic acids having 2 to 44 carbon atoms, ethylene or propylene as component B.
    • is used as a binder in adhesive preparations, sealants or redispersion powders.

    Unter einem "Copolymeren" wird im Rahmen des vorliegenden Textes ein Polymeres verstanden, das durch radikalische Polymerisation von zwei oder mehr radikalisch polymerisierbaren Monomeren erhältlich ist. Es kann sich dabei um ein statistisches Copolymeres handeln, d. h., daß die Abfolge der Monomeren keiner besonderen Ordnung unterliegt, es kann sich jedoch auch um ein alternierendes oder ein Block-Copolymeres handeln.A "copolymer" is used in the context of the present text Polymer understood that by radical polymerization of two or more radically polymerizable monomers is available. It can be a statistical copolymer, i. that is, the Sequence of the monomers is not subject to any particular order, it can However, it is also an alternating or a block copolymer act.

    Im Rahmen der vorliegenden Erfindung wird zur Herstellung der erfindungsgemäß verwendeten Copolymeren eine Komponente A und eine Komponente B copolymerisiert. Als Komponente A wird mindestens ein Ester einer mindestens difunktionellen und mindestens eine olefinisch ungesättigte Doppelbindung aufweisenden Carbonsäure mit einem Alkylenoxidaddukt eingesetzt.Within the scope of the present invention, the production of Copolymers used according to the invention have a component A and copolymerized a component B. As component A at least an ester of an at least difunctional and at least one olefinic carboxylic acid having unsaturated double bond with a Alkylene oxide adduct used.

    Als mindestens difunktionelle Carbonsäuren, die mindestens eine olefinisch ungesättigte Doppelbindung aufweisen, eignen sich beispielsweise Maleinsäure, Fumarsäure, Itaconsäure, Arconitsäure, 3,4,5,6-Tetrahydrophthalsäure, Crotonsäure, oder ein Gemisch aus zwei oder mehr davon.As at least difunctional carboxylic acids, the at least one have olefinically unsaturated double bond are suitable for example maleic acid, fumaric acid, itaconic acid, arconitic acid, 3,4,5,6-tetrahydrophthalic acid, crotonic acid, or a mixture of two or more of it.

    Um geeignete Ester herzustellen, wie sie im Rahmen der vorliegenden Erfindung als Komponente A einsetzbar sind, können die den Estem zugrundeliegenden, olefinisch ungesättigten Di- oder Polycarbonsäuren beispielsweise nur partiell verestert werden, d.h., es wird nur ein Teil der für eine Veresterung zur Verfügung stehenden Carbonsäuregruppen mit einem geeigneten Alkylenoxidaddukt verestert. Es ist darüber hinaus ebenso möglich, die Carbonsäuregruppen der Carbonsäure partiell oder vollständig mit einem Alkylenoxid umzusetzen, so daß die Esterfunktion durch Oxalkylierung gebildet wird.In order to produce suitable esters, as described in the present Invention can be used as component A, the Estem underlying olefinically unsaturated di- or polycarboxylic acids for example, are only partially esterified, i.e. only part of the available for an esterification with carboxylic acid groups esterified with a suitable alkylene oxide adduct. It is beyond that as well possible, the carboxylic acid groups of the carboxylic acid partially or completely react with an alkylene oxide so that the ester function by Oxalkylation is formed.

    Geeignete Partialester wie sie im Rahmen einer bevorzugten Ausführungsform der vorliegenden Erfindung als Komponente A eingesetzt werden, sind beispielsweise Partialester der oben genannten Carbonsäuren mit Alkylenoxidaddukten von linearen oder verzweigten, gesättigten Alkoholen, die mindestens 8 C-Atome aufweisen. Geeignete Alkohole sind beispielsweise die Fettalkohole mit mindestens 8 C-Atomen, wie sie beispielsweise durch Reduktion von natürlichen Fetten oder Ölen oder durch Reduktion von aus natürlichen Fetten oder Ölen erhältlichen Fettsäuren oder Fettsäureschnitten oder deren Derivaten, beispielsweise deren Estern mit Alkoholen mit 1 bis 4 C-Atomen, erhältlich sind.Suitable partial esters as used in a preferred embodiment of the present invention are used as component A, are, for example, partial esters of the above-mentioned carboxylic acids with alkylene oxide adducts of linear or branched, saturated alcohols, which have at least 8 carbon atoms. Suitable alcohols are for example the fatty alcohols with at least 8 carbon atoms, such as, for example by reducing natural fats or oils or by Reduction of fatty acids available from natural fats or oils or fatty acid cuts or their derivatives, for example their Esters with alcohols with 1 to 4 carbon atoms are available.

    Zur Herstellung der Alkylenoxidaddukte besonders geeignete Fettalkohole sind beispielsweise Octylalkohol, Nonylalkohol, Decylalkohol, Undecylalkohol, Dodecylalkohol, Tridecylalkohol, Tetradecylalkohol, Pentadecylalkohol, Hexadecylalkohol, Octadecylalkohol, Nonadecylalkohol, Guerbetalkohole, ungesättigte Fettalkohole wie 12-Hydroxystearylalkohol, oder höhere Homologe solcher Alkohole mit bis zu etwa 44 C-Atomen. Der Alkylrest der Fettalkohole kann linear oder verzweigt, gesättigt oder ungesättigt sein.Fatty alcohols particularly suitable for producing the alkylene oxide adducts Examples include octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, Dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, Hexadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, Guerbet alcohols, unsaturated fatty alcohols such as 12-hydroxystearyl alcohol, or higher Homologs of such alcohols with up to about 44 carbon atoms. The alkyl group the fatty alcohols can be linear or branched, saturated or unsaturated his.

    Ebenfalls als Alkoholkomponente zur Herstellung der Partialester geeignet sind beispielsweise Alkoxylenoxidaddukte von entsprechend alkoxylierbaren Verbindungen, die am Ende der durch die Alkoxylierung entstehenden Alkoxyeinheit eine OH-Gruppe aufweisen. Zur Herstellung der Alkylenoxidaddukte geeignete alkoxylierbare Verbindungen sind beispielsweise Dialkylamine mit linearen oder verzweigten, gesättigten oder ungesättigten Alkylresten mit insgesamt mindestens etwa 8 C-Atomen, lineare oder verzweigte, gesättigte oder ungesättigte Carbonsäuren, beispielsweise Fettsäuren, mit mindestens etwa 8 C-Atomen, lineare oder verzweigte, gesättigte oder ungesättigte Säureamide, beispielsweise Fettsäuremonoethanolamide, mit mindestens etwa 8 C-Atomen sowie lineare oder verzweigte, gesättigte oder ungesättigte Alkylamine, beispielsweise Fettamine, die im Alkylrest mindestens 8 C-Atome aufweisen.Also suitable as an alcohol component for the production of partial esters are, for example, alkoxylene oxide adducts of correspondingly alkoxylatable Compounds that end at the end of the alkoxylation Alkoxy unit have an OH group. For the preparation of the alkylene oxide adducts suitable alkoxylatable compounds are, for example Dialkylamines with linear or branched, saturated or unsaturated Alkyl radicals with a total of at least about 8 carbon atoms, linear or branched, saturated or unsaturated carboxylic acids, for example fatty acids, with at least about 8 carbon atoms, linear or branched, saturated or unsaturated acid amides, for example fatty acid monoethanolamides, with at least about 8 carbon atoms as well as linear or branched, saturated or unsaturated alkylamines, for example fatty amines, which in Alkyl radical have at least 8 carbon atoms.

    Unter "Alkoxylaten" oder "Alkylenoxidaddukten" werden im Rahmen des vorliegenden Textes die Umsetzungsprodukte von geeigneten Nucleophilen, beispielsweise von entsprechend funktionalisierten Ethem, Aminen, Carbonsäuren, Carbonsäureamiden oder Alkoholen mit Alkylenoxiden mit 2 bis etwa 44 C-Atomen, insbesondere etwa 8 bis etwa 24 C-Atomen, verstanden."Alkoxylates" or "alkylene oxide adducts" are used in the context of present text the reaction products of suitable nucleophiles, for example of appropriately functionalized ethers, amines, Carboxylic acids, carboxamides or alcohols with alkylene oxides 2 to about 44 carbon atoms, in particular about 8 to about 24 carbon atoms.

    In einer bevorzugten Ausführungsform der Erfindung werden zur Herstellung der Alkylenoxidaddukte Alkylenoxide mit 2 bis 4, insbesondere 2 oder 3 C-Atomen, beispielsweise Ethylenoxid oder Propylenoxid, eingesetzt. Zur Herstellung der Alkoxylierungsprodukte kann lediglich ein Alkylenoxid eingesetzt werden, es können jedoch auch zwei oder mehr Alkylenoxide eingesetzt werden. Bei einer Alkoxylierung mit mehr als zwei Alkylenoxiden kann die Alkoxylierung entweder zu einem statistischen oder einem alternierenden Copolyalkylenoxid oder zu einem Block-Copolyalkylenoxid führen. In a preferred embodiment of the invention are used to manufacture the alkylene oxide adducts alkylene oxides with 2 to 4, in particular 2 or 3 carbon atoms, for example ethylene oxide or propylene oxide, are used. Only an alkylene oxide can be used to prepare the alkoxylation products can be used, but two or more alkylene oxides can also be used be used. With alkoxylation with more than two alkylene oxides can the alkoxylation to either a statistical or a alternating copolyalkylene oxide or to a block copolyalkylene oxide to lead.

    In einer bevorzugten Ausführungsform der Erfindung wird die Alkoxylierung zum Alkylenoxidaddukt mit Ethylenoxid durchgeführt.In a preferred embodiment of the invention, the alkoxylation to the alkylene oxide adduct with ethylene oxide.

    Die im Rahmen der vorliegenden Erfindung als Alkoholkomponente einsetzbaren Alkylenoxidaddukte weisen pro Molekül im Durchschnitt mindestens eine Alkylenoxideinheit auf. In einer bevorzugten Ausführungsform der Erfindung sollte die durchschnittliche Zahl an Alkylenoxideinheiten pro Alkoholmolekül mindestens etwa 1,5, insbesondere mindestens etwa 2 betragen.Which can be used as an alcohol component in the context of the present invention Alkylene oxide adducts have an average of at least one molecule an alkylene oxide unit. In a preferred embodiment the invention should average the number of alkylene oxide units per Alcohol molecule at least about 1.5, especially at least about 2 be.

    Im Rahmen einer bevorzugten Ausführungsform der Erfindung werden als Komponente A die Partialester von olefinisch ungesättigten Dicarbonsäuren eingesetzt, die als Alkoholrest ein Alkoxylat eines Alkohols, einer Carbonsäure, eines Carbonsäureamids, eines Dialkylamins oder ein Monoalkoxylat eines Amins aufweisen. In einer weiteren bevorzugten Ausführungsform der Erfindung werden als Alkoholrest solche Alkoxylate eingesetzt, die durch Alkoxylierung der dem Alkoxylat zugrundeliegenden Verbindung mit Ethylenoxid oder Propylenoxid oder beidem erhältlich sind.In the context of a preferred embodiment of the invention, Component A is the partial ester of olefinically unsaturated dicarboxylic acids used as the alcohol residue an alkoxylate of an alcohol, a carboxylic acid, a carboxamide, a dialkylamine or a monoalkoxylate have an amine. In a further preferred embodiment In the invention, such alkoxylates are used as alcohol residues, by alkoxylation of the compound on which the alkoxylate is based are available with ethylene oxide or propylene oxide or both.

    Die den Partialestem zugrundeliegenden Alkoholreste weisen in einer bevorzugten Ausführungsform der Erfindung amphiphile Eigenschaften auf. Amphiphile Eigenschaften lassen sich häufig durch den HLB-Wert der amphiphilen Verbindung charakterisieren.The alcohol residues on which the partial esters are based have a preferred one Embodiment of the invention on amphiphilic properties. Amphiphilic properties can often be determined by the HLB value characterize amphiphilic compound.

    Im Rahmen der vorliegenden Erfindung als zur Herstellung der Partialester geeignete Alkoholkomponenten weisen beispielsweise einen HLB-Wert von etwa 1,5 bis etwa 18, beispielsweise etwa 2 bis etwa 14 oder etwa 3 bis etwa 12 auf. In the context of the present invention as for the production of partial esters suitable alcohol components have, for example, an HLB value from about 1.5 to about 18, for example about 2 to about 14 or about 3 to about 12.

    In einer bevorzugten Ausführungsform der Erfindung weist der dem Alkylenoxidaddukt zugrundeliegende nucleophile Rest etwa 12 bis etwa 24 C-Atome, beispielsweise etwa 16 bis etwa 20 C-Atome auf.In a preferred embodiment of the invention, the alkylene oxide adduct underlying nucleophilic radical from about 12 to about 24 carbon atoms, for example, about 16 to about 20 carbon atoms.

    Die entsprechenden Alkylenoxidaddukte weisen etwa 1 bis etwa 40 Alkylenoxideinheiten, beispielsweise etwa 2 bis etwa 12 Ethylenoxid- oder Propylenoxideinheiten, oder beides aufThe corresponding alkylene oxide adducts have about 1 to about 40 alkylene oxide units, for example about 2 to about 12 ethylene oxide or Propylene oxide units, or both

    Die Partialester können in Form ihrer freien Säuren eingesetzt werden, es ist jedoch ebenso möglich die Partialester als Salze, beispielsweise als Alkalimetallsalze, oder Ammoniumsalze einzusetzen. Im Rahmen einer bevorzugten Ausführungsform der Erfindung werden Partialestersalze mit leichtflüchtigen Aminen eingesetzt, beispielsweise Salze mit Butylamin oder Triethanolamin. Die Salzbildung kann vor oder nach der Polymerisation durchgeführt werden.The partial esters can be used in the form of their free acids however, the partial esters are also possible as salts, for example as Use alkali metal salts, or ammonium salts. As part of a preferred embodiment of the invention are partial ester salts with volatile amines used, for example salts with butylamine or triethanolamine. Salt formation can occur before or after the polymerization be performed.

    Neben den bereits beschriebenen Partialestem können in einer weiteren Ausführungsform der Erfindung als Komponente A Ester von ungesättigten, mindestens difunktionellen Carbonsäuren eingesetzt werden, die keine Carboxylgruppe aufweisen (Vollester), d.h., deren Carboxylgruppen vollständig verestert sind.In addition to the partial elements already described, another Embodiment of the invention as component A ester of unsaturated, at least difunctional carboxylic acids are used, which none Have carboxyl groups (full esters), i.e. their carboxyl groups are completely esterified.

    Solche Vollester weisen als Alkoholrest mindestens ein Alkylenoxidaddukt mit einem linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit mindestens etwa 8 C-Atomen auf, der zwischen dem genannten Alkylrest und der aus der ungesättigten Carbonsäure stammenden Esterfunktion mindestens 1 bis etwa 40 Alkylenoxideinheiten, beispielsweise etwa 2 bis etwa 12 Alkylenoxideinheiten, aufweist. Geeignete Alkylenoxidaddukte wurden bereits oben erwähnt. In einer bevorzugten Ausführungsform der Erfindung handelt es sich bei den Alkylenoxideinheiten um Ethylenoxideinheiten oder Propylenoxideinheiten oder deren Gemisch, insbesondere jedoch um Ethylenoxideinheiten.Such full esters have at least one alkylene oxide adduct as the alcohol residue with a linear or branched, saturated or unsaturated alkyl radical with at least about 8 carbon atoms between the above Alkyl radical and the ester function derived from the unsaturated carboxylic acid at least 1 to about 40 alkylene oxide units, for example about 2 to about 12 alkylene oxide units. Suitable alkylene oxide adducts have already been mentioned above. In a preferred embodiment the invention is the alkylene oxide units Ethylene oxide units or propylene oxide units or a mixture thereof, but especially ethylene oxide units.

    Unter einem HLB-Wert wird ein Maß für die Wasser- bzw. Öllöslichkeit von vorwiegend nichtionischen Tensiden verstanden. Insbesondere für Ethoxylate und deren Ester gilt die Formel HLB = (E + P) / 5, wobei E für die Zahl der Etyhlenoxideinheiten und P für die Zahl an Propylenoxideinheiten (Angabe in Gew.-%) im Molekül stehen. Der HLB-Wert eines Tensid- oder Emulgatorgemischs läßt sich aus den Werten seiner Bestandteile additiv berechnen. Ausführliche Listen von HLB-Werten von im Handel erhältlichen Emulgatoren finden sich beispielsweise bei Fiedler, Lexikon der Hilfsstoffe für Pharmazie, Kosmetik oder angrenzende Gebiete oder bei Kirk-Othmer (3.) 8, 910-918.An HLB value is a measure of the water or oil solubility of mainly understood nonionic surfactants. Especially for Ethoxylates and their esters have the formula HLB = (E + P) / 5, where E is the number of ethylene oxide units and P for the number of propylene oxide units (Expressed in% by weight) in the molecule. The HLB value of a surfactant or emulsifier mixture can be determined from the values of its components calculate additively. Detailed lists of HLB values from retailers Available emulsifiers can be found, for example, at Fiedler, Lexikon of auxiliaries for pharmacy, cosmetics or related areas or at Kirk-Othmer (3.) 8, 910-918.

    Die Herstellung der als Komponente A einsetzbaren Halb- oder Vollester erfolgt nach den üblichen Regeln der organischen Chemie und ist dem Fachmann bekannt. In einer bevorzugten Ausführungsform der Erfindung wird der Halbester aus einem Carbonsäureanhydrid durch Zugabe des entsprechenden Alkylenoxidaddukts gebildet. Wenn als Komponente A ein Halbester eingesetzt werden soll, so kann die Bildung des Halbesters beispielsweise in situ vor oder sogar während der Copolymerisation der Komponenten A und B erfolgen, indem man ein entsprechendes Carbonsäureanhydrid und ein entsprechendes Alkylenoxidaddukt oder ein Gemisch aus zwei oder mehr Alkylenoxidaddukten in der bereits vorgelegten Komponente B löst. The production of the half or full esters which can be used as component A. takes place according to the usual rules of organic chemistry and is Known specialist. In a preferred embodiment of the invention the half-ester is made from a carboxylic anhydride by adding the corresponding alkylene oxide adduct formed. If as component A a Half ester should be used, for example, the formation of the half ester in situ before or even during the copolymerization of the Components A and B are made by using an appropriate carboxylic anhydride and a corresponding alkylene oxide adduct or a mixture from two or more alkylene oxide adducts in the previously submitted Component B triggers.

    Als Komponente B wird im Rahmen der vorliegenden Erfindung mindestens ein weiteres radikalisch polymerisierbares Monomeres eingesetzt. Geeignete Monomere sind beispielsweise die Vinylester von Carbonsäuren mit etwa 2 bis etwa 44 C-Atomen. Geeignete Vinylester sind beispielsweise Vinylacetat, Vinylpropionat, Vinylbutyrat, die Vinylester der isomeren Pentansäuren, Hexansäuren, Heptansäuren, Oktansäuren, Nonansäuren, Dekansäuren und deren höhere Homologe. Ebenfalls als Komponente B geeignet sind beispielsweise Ethylen oder Propylen.As component B in the context of the present invention at least one further radically polymerizable monomer used. Suitable monomers are, for example, the vinyl esters of Carboxylic acids with about 2 to about 44 carbon atoms. Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, the vinyl esters the isomeric pentanoic acids, hexanoic acids, heptanoic acids, octanoic acids, Nonanoic acids, decanoic acids and their higher homologues. Also as Component B is suitable, for example, ethylene or propylene.

    Bei der Copolymerisation der Komponenten A und B liegt die Komponente A im zu copolymerisierenden Polymerisationsgemisch in einer Menge von etwa 0,01 bis 70 Gew.-%, beispielsweise in einer Menge von 0,5 bis etwa 50 Gew.-% oder etwa 1 bis etwa 20 Gew.-%, in Bezug auf die gesamte Mischung, vor. Im Rahmen einer weiteren bevorzugten Ausführungsform der Erfindung wird als Komponente B Vinylacetat, Vinylpropionat, Vinyllaurat oder Vinylversatat, insbesondere Vinylacetat, eingesetzt.When components A and B are copolymerized, the component lies A in the polymerization mixture to be copolymerized in an amount of about 0.01 to 70% by weight, for example in an amount of 0.5 to about 50% by weight or about 1 to about 20% by weight, based on the total Mixture, before. In a further preferred embodiment The invention uses as component B vinyl acetate, vinyl propionate, Vinyl laurate or vinyl versatate, especially vinyl acetate, is used.

    In einer weiteren bevorzugten Ausführungsform der Erfindung wird als Komponente B ein Gemisch aus zwei oder mehr copolymersierbaren Monomeren eingesetzt. Geeignet sind beispielsweise Gemische von Vinylacetat Vinylpropionat, Vinyllaurat oder Vinylversatat, jeweils mit einem oder mehreren der weiteren oben angegebenen Monomeren.In a further preferred embodiment of the invention, as Component B is a mixture of two or more copolymerizable Monomers used. Mixtures of Vinyl acetate vinyl propionate, vinyl laurate or vinyl versatate, each with one or more of the other monomers specified above.

    Werden als Komponente B Gemische aus zwei oder mehr Monomeren eingesetzt, so enthält das Gemisch im Rahmen einer bevorzugten Ausführungsform mindestens einen Vinylester einer Carbonsäure, insbesondere Vinylacetat. Der Anteil an Vinylester einer Carbonsäure sollte in einem solchen Gemisch mindestens etwa 30 Gew.-% betragen.As component B, mixtures of two or more monomers used, the mixture contains a preferred Embodiment at least one vinyl ester of a carboxylic acid, especially vinyl acetate. The proportion of vinyl ester of a carboxylic acid should be at least about 30% by weight in such a mixture.

    Die Herstellung der erfindungsgemäß verwendeten Copolymeren kann nach den üblichen Verfahren der radikalischen Polymerisation erfolgen. Bevorzugt wird die Polymerisation als Emulsions- oder Suspensionspolymerisation in Wasser durchgeführt. Die Polymerisationstemperatur beträgt vorzugsweise etwa 50 bis etwa 90°C, insbesondere etwa 75 bis etwa 85°C. The copolymers used according to the invention can be prepared carried out according to the usual methods of radical polymerization. The polymerization is preferred as an emulsion or Suspension polymerization carried out in water. The Polymerization temperature is preferably about 50 to about 90 ° C, especially about 75 to about 85 ° C.

    Als Emulgatoren können die im Rahmen der Emulsionspolymerisation üblicherweise eingesetzten Emulgatoren verwendet werden. Gegebenenfalls kann ein Schutzkolloid zugesetzt werden.As emulsifiers, they can be used in the context of emulsion polymerization Usually used emulsifiers can be used. If necessary, a protective colloid can be added.

    Als Startermoleküle, d.h., zur Initiierung der radikalischen Polymerisation, werden übliche wasserlösliche Radikalstarter zugegeben, bei der Suspensionspolymerisation können lipophile Radikalstarter zugegeben werden.As starter molecules, i.e. to initiate radical polymerization, usual water-soluble radical initiators are added, in which Suspension polymerization can add lipophilic radical initiators become.

    Ebenfalls Gegenstand der Erfindung ist die Verwendung des Copolymeren, wobei zur Herstellung des Copolymeren mindestens zwei Komponenten A und B copolymerisiert werden, wobei

  • a) mindestens ein Ester einer mindestens difunktionellen und mindestens eine olefinisch ungesättigte Doppelbindung aufweisenden Carbonsäure mit einem Alkylenoxidaddukt als Komponente A und
  • b) mindestens ein weiteres radikalisch polymerisierbares Monomeres als Komponente B
    • eingesetzt wird.The invention also relates to the use of the copolymer, at least two components A and B being copolymerized to prepare the copolymer, where
  • a) at least one ester of an at least difunctional and at least one olefinically unsaturated double bond carboxylic acid with an alkylene oxide adduct as component A and
  • b) at least one further radically polymerizable monomer as component B.
    • is used.

    Die erfindungsgemäß verwendeten Copolymeren werden beispielsweise in Klebstoffzubereitungen wie Dispersionsklebstoffen, Haftklebstoffen, bei der Herstellung von Klebstoffilmen oder zur Herstellung von Redispersionspulvern eingesetzt. The copolymers used according to the invention are, for example in adhesive preparations such as dispersion adhesives, pressure sensitive adhesives, at the production of adhesive films or for the production of Redispersion powders used.

    Gegenstand der Erfindung ist daher auch die Verwendung des Copolymeren in einer Zubereitung, die mindestens 0,1 Gew.-% des Copolymeren enthält.The invention therefore also relates to the use of the Copolymers in a preparation containing at least 0.1% by weight of the Contains copolymers.

    Wenn zur Herstellung der Komponente A Alkylenoxidaddukte mit olefinisch ungesättigten Doppelbindungen eingesetzt werden, so können die erfindungsgemäß verwendeten Zubereitungen zusätzlich noch Sikkative enthalten.When using alkylene oxide adducts to produce component A. olefinically unsaturated double bonds can be used the preparations used according to the invention additionally Desiccant included.

    Eine erfindungsgemäß verwendete Zubereitung kann neben den erfindungsgemäßen Copolymeren noch bis zu etwa 50 Gew.-% an üblichen Zusatzstoffen enthalten. Solche Zusatzstoffe können beispielsweise die Klebeigenschaften, das Alterungsverhalten, den Abbindevorgang oder die Adhäsion beeinflussen. So kann der Klebstoff beispielsweise sogenannte Tackifier-Harze enthalten, die sich in der Regel in natürliche und synthetische (Kunstharze) unterteilen lassen. Hierzu zählen beispielsweise Alkydharze, Epoxydharze, Melaminharze, Phenolharze, Urethanharze, Kohlenwasserstoffharze sowie natürliche Harze wie Colophonium, Holzterpentinöl und Tallöl. Zu den synthetischen Harzen Kohlenwasserstoffharze, Ketonharze, Cumaron-Indenharze, Isocyanatharze und Terpen-Phenolharze.A preparation used according to the invention can in addition to copolymers according to the invention still up to about 50 wt .-% contain usual additives. Such additives can for example the adhesive properties, the aging behavior, the Affect the setting process or the adhesion. So the glue can for example, contain so-called tackifier resins, which are usually divided into natural and synthetic (synthetic resins). For this include, for example, alkyd resins, epoxy resins, melamine resins, Phenolic, urethane, hydrocarbon and natural Resins such as rosin, wood turpentine and tall oil. To the synthetic Resins hydrocarbon resins, ketone resins, coumarone indene resins, Isocyanate resins and terpene phenolic resins.

    Weiterhin können die erfindungsgemäß als Klebstoffe verwendeten Zubereitungen Lösemittel enthalten. Als Lösemittel geeignet sind beispielsweise ein- oder mehrwertige Alkohole mit etwa 2 bis etwa 10 C-Atomen.Furthermore, the adhesives used according to the invention can be used Preparations contain solvents. Are suitable as solvents for example monohydric or polyhydric alcohols with about 2 to about 10 carbon atoms.

    Weiterhin können die erfindungsgemäß als Klebstoffe verwendeten Zubereitungen Entschäumer enthalten. Als Entschäumer geeignet sind beispielsweise Entschäumer auf Fettalkoholbasis oder auf Silikonbasis. Furthermore, the adhesives used according to the invention can be used Preparations contain defoamers. Are suitable as defoamers for example defoamer based on fatty alcohol or silicone.

    Weiterhin können die erfindungsgemaß als Klebstoff verwendeten Zubereitungen Schutzkolloide wie Polyvinylpyrrolidone, Polyvinylalkohole oder Cellulose oder Cellulosederivate enthalten.Furthermore, can be used as an adhesive according to the invention Preparations protective colloids such as polyvinylpyrrolidones, polyvinyl alcohols or contain cellulose or cellulose derivatives.

    Weiterhin kann die erfindungsgemäß als Klebstoff verwendete Zubereitung als Zusatzstoffe Stabilisatoren oder Antioxidantien enthalten. Hierzu zählen in der Regel die Phenole, beispielsweise die sterisch gehinderten Phenole hohen Molekulargewichts, polyfunktionelle Phenole, schwefelund phosphorhaltige Phenole oder Amine. Als Stabilisatoren geeignet sind beispielsweise Hydrochinon, Hydrochinonmethylether 2,3-(Di-tert.-butyl)hydrochinon, 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydro-xybenzyl)benzol; Pentaerythrittetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionat; n-Octadecyl-3,5-di-tert-butyl-4-hydroxyphenyl)propionat; 4,4-Methylenbis(2,6-di-tert-butyl-phenol); 4,4-Thiobis(6-tert-butyl-o-cresol); 2,6-Ditert-butylphenol; 6-(4-Hydroxyphenoxy)-2,4-bis(n-octyl-thio)-1,3,5-triazin; Di-n-Octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate; 2-(n-Octylthio)ethyl-3,5-di-tert-butyl-4-hydroxybenzoat; und Sorbithexa[3-(3,5-ditert-butyl-4-hydro-xyphenyl)propionat]; sowie p-Hydroxydiphenylamin oder N,N'-Diphenylen-diamin oder Phenothiazin.Furthermore, the preparation used as an adhesive according to the invention can contain stabilizers or antioxidants as additives. For this usually include the phenols, for example the sterically hindered High molecular weight phenols, polyfunctional phenols, sulfur and phosphorus-containing phenols or amines. Are suitable as stabilizers for example hydroquinone, hydroquinone methyl ether 2,3- (di-tert-butyl) hydroquinone, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydro xybenzyl-) benzene; Pentaerythritol tetrakis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; n-octadecyl-3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4,4-methylenebis (2,6-di-tert-butyl-phenol); 4,4-thiobis (6-tert-butyl-o-cresol); 2,6-di-tert-butyl phenol; 6- (4-hydroxyphenoxy) -2,4-bis (n-octyl-thio) -1,3,5-triazine; Di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonates; 2- (n-octylthio) ethyl-3,5-di-tert-butyl-4-hydroxybenzoate; and sorbitol hexa [3- (3,5-di-tert-butyl-4-hydro-xyphenyl) propionate]; and p-hydroxydiphenylamine or N, N'-diphenylene diamine or phenothiazine.

    Die erfindungsgemäß als Klebstoff verwendete Zubereitung kann weiterhin Weichmacher wie Benzoatweichmacher, Phosphatweichmacher, flüssige Harzderivate oder pflanzliche und tierische Öle enthalten. Geeignet sind beispielsweise Sucrosebenzoat, Diethylenglykoldibenzoat und/oder Diethylenglykolbenzoat, bei dem etwa 50 bis etwa 95% aller Hydroxylgruppen verestert worden sind, Phosphat-Weichmacher, beispielsweise t-Butylphenyldiphenylphosphat, Polyethylenglykole und deren Derivate, beispielsweise Diphenylether von Poly(ethylenglykol), flüssige Harzderivate, beispielsweise der Methylester von hydriertem Harz, pflanzliche und tierische Öle, beispielsweise Glycerinester von Fettsäuren und deren Polymerisationsprodukte.The preparation used as an adhesive according to the invention can plasticizers such as benzoate plasticizers, phosphate plasticizers, contain liquid resin derivatives or vegetable and animal oils. For example, sucrose benzoate and diethylene glycol dibenzoate are suitable and / or diethylene glycol benzoate, in which about 50 to about 95% of all Hydroxyl groups have been esterified, phosphate plasticizers, for example t-butylphenyl diphenyl phosphate, polyethylene glycols and their derivatives, for example diphenyl ether of poly (ethylene glycol), liquid resin derivatives, for example the methyl ester of hydrogenated resin, vegetable and animal oils, for example glycerol esters of fatty acids and their Polymerization products.

    Ebenfalls geeignet sind Weichmacher auf Basis von Phthalsäure, insbesondere die Alkylphthalate.Plasticizers based on phthalic acid are also suitable, especially the alkyl phthalates.

    Die erfindungsgemäß als Klebstoff verwendete Zubereitung kann weiterhin Farbstoffe wie Titandioxid, Füllstoffe wie Gips, Talkum, Ton und dergleichen sowie Pigmente enthalten.The preparation used as an adhesive according to the invention can furthermore dyes such as titanium dioxide, fillers such as gypsum, talc, clay and the like and contain pigments.

    Weiterhin können die erfindungsgemäß als Klebstoffe verwendeten Zubereitungen Emulgatoren oder Stabilisatoren oder deren Gemisch enthalten. Als Emulgatoren eignen sich in der Regel Tenside, die eine hydrophile und eine hydrophobe Gruppe aufweisen. Es kann sich dabei um anionische Emulgatoren, kationische Emulgatoren oder amphotere Emulgatoren handeln. Geeignet sind beispielsweise Kohlenwasserstoffemulgatoren mit etwa 6 bis etwa 22 Kohlenstoffatomen, wobei die Kohlenwasserstoffkette verzweigt, unverzweigt, gesättigt, ungesättigt, substituiert, aliphatisch oder aromatisch sein kann.Furthermore, the adhesives used according to the invention can be used Preparations emulsifiers or stabilizers or a mixture thereof contain. Suitable emulsifiers are generally surfactants, the one have hydrophilic and a hydrophobic group. It can happen anionic emulsifiers, cationic emulsifiers or amphoteric Act emulsifiers. For example, are suitable Hydrocarbon emulsifiers with about 6 to about 22 carbon atoms, where the hydrocarbon chain is branched, unbranched, saturated, can be unsaturated, substituted, aliphatic or aromatic.

    Ein weiterer Gegenstand der Erfindung ist vorzugsweise die Verwendung als Bindemittel in Klebstoffzubereitungen.Another object of the invention is preferably the use as a binder in adhesive preparations.

    Die Erfindung wird nachfolgend durch Beispiele näher erläutert. The invention is explained in more detail below by examples.

    Experimenteller TeilExperimental part Herstellung von Maleinsäure-C12/14-Fettalkohol x 4 EO-halbesterProduction of maleic acid C12 / 14 fatty alcohol x 4 EO half esters

    367 g Maleinsäureanhydrid (3,74 mol) und 800 g Dehydol LS 4 (C12/14-Fettalkohol x 4 EO, 3,74 mol) werden unter Stickstoff 3 Stunden bei 120 °C gerührt. Nach dem Abkühlen erhält man 1150 g des Halbesters als pastöse Masse. SZ = 139 mg KOH/g 367 g of maleic anhydride (3.74 mol) and 800 g of dehydol LS 4 (C12 / 14 fatty alcohol x 4 EO, 3.74 mol) are stirred under nitrogen at 120 ° C. for 3 hours. After cooling, 1150 g of the half ester are obtained as a pasty mass. SZ = 139 mg KOH / g

    Beispiel 1example 1 Herstellung einer Copolymer-Dispersion aus Vinylacetat und Maleinsäre-C12/14-Fettalkohol x 4 EO-halbesterPreparation of a copolymer dispersion from vinyl acetate and maleic acid C12 / 14 fatty alcohol x 4 EO-half

    In 862 g einer auf 75 - 80 °C erhitzten Vorlösung von 809 g entsalztem Wasser, 1,8 g Nonylphenol mit 9,5 mol EO, 20 g Sulfobernsteinsäurebis-2-ethylhexylester-Natriumsalz, 1,4 g Natriumhydrogencarbonat und 30 g teilverseiftem Polyvinylalkohol werden unter Rühren 16 g einer Starterlösung aus 6 g Kaliumperoxodisulfat und 110 g Wasser gegeben. Dann werden unter Rückfluß bei dieser Temperatur über 5 h gleichzeitig die restliche Starterlösung (100 g) und die Monomerlösung bestehend aus 914 g Vinylacetat und 102 g des Maleinsäurehalbester zugetropft. Bei Dosierung wird darauf geachtet, daß die Temperatur 85 °C nicht übersteigt. Nach Abtrennung der grobteiligen Bestandteile durch Filtration erhält man ca. 1950 g einer Polymerdispersion mit folgenden Eigenschaften: pH-Wert 2,5 bis 3,5 Festkörper ca. 55 % Viskosität 11.000 mPas In 862 g of a preliminary solution of 809 g of demineralized water heated to 75-80 ° C., 1.8 g of nonylphenol with 9.5 mol of EO, 20 g of bis-2-ethylhexyl sodium salt, 1.4 g of sodium hydrogen carbonate and 30 g of partially saponified polyvinyl alcohol 16 g of a starter solution of 6 g of potassium peroxodisulfate and 110 g of water are added with stirring. Then the remaining starter solution (100 g) and the monomer solution consisting of 914 g of vinyl acetate and 102 g of the maleic acid half-ester are simultaneously added dropwise under reflux at this temperature for 5 h. When dosing, ensure that the temperature does not exceed 85 ° C. After the coarse particles have been separated off by filtration, about 1950 g of a polymer dispersion having the following properties are obtained: PH value 2.5 to 3.5 solid approx. 55% viscosity 11,000 mPas

    Beispiel 2Example 2 Herstellung einer Homopolymer-Dispersion mit VinylacetatProduction of a homopolymer dispersion with vinyl acetate

    In 893,2 g einer auf 75-80°C erhitzten Vorlösung von 799 g entsalztem Wasser, 1,8 g Nonylphenol mit 9,5 mol EO, 20 g Sulfobernsteinsäurebis-2-ethylhexylester-Natrium-Salz, 1,4 g Natriumhydrogencarbonat und 71 g teilverseiftem Polyvinylalkohol werden unter Rühren 10 g einer Starterlösung aus 4 g Kaliumperoxodisulfat und 76 g Wasser gegeben. Dann werden unter Rückfluß bei dieser Temperatur über 5 h gleichzeitig die restliche Starterlösung (70 g) und 816 g Vinylacetat zugetropft. Bei Dosierung wird darauf geachtet, daß die Temperatur 85°C nicht übersteigt. Nach Abtrennung der grobteiligen Bestandteile durch Filtration erhält man ca. 1760 g einer Polymerdispersion mit folgenden Eigenschaften: pH-Wert 5,5 Festkörper ca. 51% Viskosität 9.000 mPas In 893.2 g of a preliminary solution heated to 75-80 ° C. of 799 g of deionized water, 1.8 g of nonylphenol with 9.5 mol of EO, 20 g of sulfosuccinic acid bis-2-ethylhexyl ester sodium salt, 1.4 g of sodium hydrogen carbonate and 71 g of partially saponified polyvinyl alcohol are added with stirring 10 g of a starter solution composed of 4 g of potassium peroxodisulfate and 76 g of water. Then the remaining starter solution (70 g) and 816 g of vinyl acetate are simultaneously added dropwise at this temperature over 5 h. When dosing, ensure that the temperature does not exceed 85 ° C. After the coarse particles have been separated off by filtration, approximately 1760 g of a polymer dispersion having the following properties are obtained: PH value 5.5 solid approx. 51% viscosity 9,000 mPas

    Vergleich der Eigenschaften:Comparison of properties:

    Copolymer- DispersionCopolymer dispersion
    (Beispiel 1)(Example 1)     Homopolymer- DispersionHomopolymer dispersion
    (Beispiel 2)(Example 2)     D1D1 12 N/mm2 12 N / mm 2 11,2 N/mm2 11.2 N / mm 2 Reißkrafttensile force 4,5 N/mm2 4.5 N / mm 2 15 N/mm2 15 N / mm 2 Reißdehnungelongation at break 2200 %2200% 20 bis 30 %20 to 30%

    Claims (9)

    1. Use of the copolymer obtainable by free-radical copolymerization of at least two components A and B, where
      a) at least one ester of an at least difunctional carboxylic acid containing at least one olefinically unsaturated double bond with an alkylene oxide adduct is used as component A and
      b) at least one further free-radically polymerizable monomer from the group consisting of vinyl esters of carboxylic acids having 2 to 44 carbon atoms, ethylene and propylene is used as component B,
      as binders in adhesive formulations, sealants or redispersible powders.
    2. Use according to Claim 1, characterized in that a partial ester containing at least one carboxyl group and at least one alkylene oxide adduct having at least 8 carbon atoms is used as component A.
    3. Use according to Claim 1 or 2, characterized in that an ester of maleic acid, fumaric acid, citraconic acid, itaconic acid, aconitic acid, 3,4,5,6-tetrahydrophthalic acid, or a mixture of two or more thereof, is used as component A.
    4. Use according to one of Claims 1 to 3, characterized in that at least one alkylene oxide adduct in component A has an HLB of from about 2 to about 20.
    5. Use according to one of Claims 1 to 4, characterized in that a vinyl ester of carboxylic acids having 2 to 44 carbon atoms is used as component B.
    6. Use according to one of Claims 1 to 5, characterized in that on copolymerization from 0.1 to 70% by weight of component A is present in the polymerization mixture.
    7. Use according to one of Claims 1 to 6, characterized in that a copolymer is prepared by copolymerizing at least two components A and B, where
      a) at least one ester of an at least difunctional carboxylic acid containing at least one olefinically unsaturated double bond with an alkylene oxide adduct is used as component A and
      b) at least one further free-radically polymerizable monomer is used as component B.
    8. Use according to Claim 1 to 7 in a formulation containing at least 0.1% by weight of a copolymer.
    9. Use of a copolymer according to one of Claims 1 to 8 as a binder in adhesive formulations.
    EP00936690A 1999-04-16 2000-04-07 Copolymers with amphiphilic sub-units, a method for producing the same and the use thereof Expired - Lifetime EP1173490B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19917356 1999-04-16
    DE19917356 1999-04-16
    PCT/EP2000/003141 WO2000063264A1 (en) 1999-04-16 2000-04-07 Copolymers with amphiphilic sub-units, a method for producing the same and the use thereof

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    EP1173490B1 true EP1173490B1 (en) 2004-07-14

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    TW200940571A (en) * 2008-02-07 2009-10-01 Constr Res & Tech Gmbh Vinyl ester/maleic acid derivative copolymers
    US8192520B2 (en) * 2009-10-05 2012-06-05 Specialty Fertilizer Products, Llc Enhanced fertilizer products with polymer adjuvants
    US7686863B1 (en) 2009-10-05 2010-03-30 Specialty Fertilizer Products, Llc Gypsum fertilizer products with polymer adjuvants
    US9145340B2 (en) 2012-08-13 2015-09-29 Verdesian Life Sciences, Llc Method of reducing atmospheric ammonia in livestock and poultry containment facilities
    US9961922B2 (en) 2012-10-15 2018-05-08 Verdesian Life Sciences, Llc Animal feed and/or water amendments for lowering ammonia concentrations in animal excrement
    US11254620B2 (en) 2013-08-05 2022-02-22 Verdesian Life Sciences U.S., Llc Micronutrient-enhanced polymeric seed coatings
    TW201522390A (en) 2013-08-27 2015-06-16 特級肥料產品公司 Polyanionic polymers
    CA2923561C (en) 2013-09-05 2022-05-03 Verdesian Life Sciences, Llc Polymer-boric acid compositions
    WO2015179687A1 (en) 2014-05-21 2015-11-26 Verdesian Life Sciences, Llc Polymer soil treatment compositions including humic acids
    WO2015179552A1 (en) 2014-05-22 2015-11-26 Verdesian Life Sciences, Llc Polymeric compositions
    GB201620952D0 (en) * 2016-12-09 2017-01-25 Tremco Illbruck Coatings Ltd Sealants for insulting glass units

    Family Cites Families (7)

    * Cited by examiner, † Cited by third party
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    US3657175A (en) * 1969-06-26 1972-04-18 Standard Brands Chem Ind Inc Carboxylic acid latices providing unique thickening and dispersing agents
    US4075411A (en) 1975-05-23 1978-02-21 Haven Industries, Inc. Vinyl-polymerizable surfactive monomers
    AU527072B2 (en) * 1978-11-27 1983-02-17 Dow Chemical Company, The Aqueous emulsion copolymer
    WO1995011341A1 (en) * 1993-10-18 1995-04-27 Monsanto Company Improved polymer solution for sizing paper
    DE19609789A1 (en) * 1996-03-13 1997-09-18 Henkel Kgaa Process for the preparation of co-oligomers and their use in the finishing of leather
    ES2193418T3 (en) * 1996-12-13 2003-11-01 Henkel Kgaa POLYMER BASED ON A CONJUGATED DIEN AND A DENOPHILE COMPONENT.
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    EP1173490A1 (en) 2002-01-23
    ES2225148T3 (en) 2005-03-16
    TR200102510T2 (en) 2001-12-21
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    DE50007078D1 (en) 2004-08-19
    ATE271078T1 (en) 2004-07-15

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